Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
  • C09B29/08—Amino benzenes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
  • C09B29/08—Amino benzenes
  • C09B29/0805—Amino benzenes free of acid groups
  • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
  • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
  • C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
  • C09B29/0813—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by OH, O-C(=X)-R, O-C(=X)-X-R, O-R (X being O,S,NR; R being hydrocarbonyl)
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
  • C09B29/08—Amino benzenes
  • C09B29/0805—Amino benzenes free of acid groups
  • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
  • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B41/00—Special methods of performing the coupling reaction
  • C09B41/001—Special methods of performing the coupling reaction characterised by the coupling medium
  • C09B41/005—Special methods of performing the coupling reaction characterised by the coupling medium containing low molecular weight dispersing agents; containing surface active polythylene gylcols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
  • C09B67/0015—Influencing the physical properties by treatment with a liquid, e.g. solvents of azoic pigments

Definitions

• the present invention relates to a process for producing a monoazodye. More particularly, it relates to a process for producing a monoazodye, whereby the productivity is improved.
• Monoazo compounds of the following structural formulas have long been known as disperse dyes.
• X is halogen.
• These monoazo compounds can be prepared by diazotizing the respective anilines as their diazo components by conventional methods, followed by coupling with the respective aniline derivatives as their coupling components in an aqueous medium.
• the cakes thereby obtained have a drawback that when they are used as disperse dyes, the dispersibility as dyes and the stability with time are poor.
• the present invention provides a process for producing a monoazodye of the following formula (III): wherein X 1 is nitro or halogen, X 2 is halogen, R 1 is lower alkoxy, R 2 is lower alkyl, each of R 3 and R 4 , which are independent of each other, is alkyl, cyanoalkyl or alkylcarbonyloxyalkyl, and each of m and n, which are independent of each other, is 0 or 1, which comprises diazotizing an aniline derivative of the following formula (I): wherein X 1 and X 2 are as defined above, followed by coupling with an aniline derivative of the following formula (II): wherein R 1 , R 2 , R 3 , R 4 , m and n are as defined above, wherein a reaction mixture obtained by the coupling reaction is heat-treated in the presence of a polyoxyethylene higher fatty acid ester type nonionic surfactant represented by the formula, R-COO-(C 2 H 4 O)
• CA, 107, 1987, Abstr. No. 794 78; CA, 112, 1990, Abstr. No. 181 386; CA, 76, 1972, Abstr. No. 101 209; EP-A-0 363 730; and FR-A-2 057 480 dislose processes for producing a monoazodye analogous to the present invention, however by using a polyoxyethylene ether as a surfactant.
• the aniline derivative of the formula (I) includes, for example, 2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-bromoaniline, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2,6-difluoro-4-nitroaniline, 2,6-diiodo-4-nitroaniline and 2-bromo-6-chloro-4-nitroaniline.
• the diazotization reaction is conducted usually by dissolving the aniline derivative of the formula (I) in nitrosyl sulfuric acid at a temperature of from 10 to 40°C, preferably from 20 to 30°C, and stirring the solution for from 3 to 5 hours. After completion of the diazotization reaction, the diazotized aniline derivative is subjected to the coupling reaction with an aniline derivative of the above formula (II).
• R 1 is lower alkoxy such as methoxy or ethoxy.
• R 2 is lower alkyl such as methyl or ethyl, and methyl is preferred.
• R 3 and R 4 which are independent of each other, is alkyl such as methyl, ethyl, propyl or butyl, preferably lower alkyl, cyanoalkyl such as cyanoethyl or cyanopropyl, preferably cyano lower alkyl, alkylcarbonyloxyalkyl such as methylcarbonyloxyethyl, ethylcarbonyloxyethyl, methylcarbonyloxypropyl or ethylcarbonyloxypropyl, preferably lower alkylcarbonyloxy lower alkyl.
• m and n which are independent of each other, is 0 or 1.
• "lower” means C 1-4 .
• aniline derivatives of the formula (II) particularly preferred are the following compounds.
• the coupling reaction is conducted usually in an aqueous medium under an acidic condition.
• the coupling reaction can be conducted by dissolving the compound of the formula (II) in an aqueous medium such as hydrochloric acid, sulfuric acid or acetic acid and mixing thereto the diazotized solution obtained by the above-mentioned diazotization reaction under stirring.
• a nitrous acid-removing agent such as sulfamic acid
• the coupling reaction is conducted usually at a temperature of from -10 to +20°C, preferably from -5 to +5°C, and the reaction time is usually from 1 to 10 hours.
• each of X 13 , X 21 , X 22 and X 23 is chlorine or bromine, and R 11 is methoxy or ethoxy.
• the reaction mixture containing crystals of this monoazo compound is subjected to heat treatment in the presence of the specific surfactant. If a cake is recovered by filtration without conducting the heat treatment, the volume of the cake will be very large, and the filtration property tends to be poor, whereby the compound tends to undergo hydrolysis during the filtration. Further, a powdery dye obtained by finely pulverizing the mixture by a pulverizer such as a sand mill by using an anion dispersant, will be poor in the dispersibility and the stability with time.
• the above heat treatment is conducted usually by stirring at a temperature of from 50 to 90°C, preferably from 50 to 70°C, for from 0.5 to 3 hours, preferably from 1 to 2 hours. If the heating temperature is too low, no adequate effect of the heat treatment will be obtained. On the other hand, if the heating temperature is too high, decomposition of the dye tends to take place, such being undesirable. If the heating time is too short, no adequate effect of the heat treatment will be obtained, and if it is too long, such is uneconomical and undesirable.
• the feature of the present invention resides in the presence of a polyoxyethylene higher fatty acid ester type nonionic surfactant during the above heat treatment. Namely, by the presence of this surfactant, it will be possible to continuously heat-treat the mixture after completion of the coupling reaction, and it is possible to improve the filtration property of the heat-treated mixture and to reduce the volume of the cake, whereby filtration of the cake can be efficiently conducted. Besides, the obtained compound will have good stability with time as a disperse dye.
• the polyoxyethylene higher fatty acid ester type nonionic surfactant to be used in the present invention is an ester of a C 11-21 saturated or unsaturated aliphatic acid with a polyoxyethylene glycol and is represented by the following formula (IV): R-COO-(C 2 H 4 O) n -H wherein R is a C 10-20 saturated or unsaturated aliphatic hydrocarbon group, and n is a positive integer.
• the higher fatty acid constituting the nonionic surfactant is preferably a C 16-19 aliphatic acid. Specifically, it may be n-hexadecanoic acid (C 15 H 31 COOH), n-heptadecanoic acid (C 16 H 33 COOH), n-octadecanoic acid (C 17 H 35 COOH), n-nonadecanoic acid (C 18 H 37 COOH), 9-hexadecenoic acid ((C 15 H 29 COOH), 6-octadecenoic acid (C 17 H 33 COOH), 9-octadecenoic acid (C 17 H 33 COOH) or 9,12-octadecadienoic acid (C 17 H 31 COOH).
• the polyoxyethylene glycol is preferably the one having a molecular weight such that the nonionic surfactant formed by esterification will have a HLB (hydrophilic-lipophilic balance) within a range of from 11 to 16, preferably from 12 to 15.
• HLB hydrophilic-lipophilic balance
• HLB hydrophilic-lipophilic balance
• the above nonionic surfactant is used usually in an amount of from 1 to 10 wt%, preferably from 2 to 5 wt%, based on the monoazo compound to be produced. If the amount of the nonionic surfactant is too small, no adequate effect for solving the problem will be obtained. On the other hand, if the amount is too large, no additional effect will be obtained, and such is not economical. Therefore, it is advisable that the amount is within the above range.
• the nonionic surfactant may be added to the reaction mixture after completion of the coupling reaction. However, if the nonionic surfactant is present during the coupling reaction, the yield of the coupling reaction itself may sometimes be improved in addition to the above-mentioned effects. Therefore, it is particularly preferred that the nonionic surfactant is present even during the coupling reaction.
• the reaction mixture after the above heat treatment is then filtered by a conventional method by means of a filtration machine such as a filter press, a Nutsche funnel or a centrifugal separator, to recover the cake.
• a filtration machine such as a filter press, a Nutsche funnel or a centrifugal separator
• the coupling reaction is followed by heat treatment of the reaction mixture in the presence of a polyoxyethylene higher fatty acid ester type nonionic surfactant.
• a polyoxyethylene higher fatty acid ester type nonionic surfactant By the presence of such a surfactant, heat treatment can be conducted without filtration of the reaction mixture after the coupling reaction, and thus the productivity is good.
• foaming during the heat treatment can be minimized, whereby overflow from the reactor can be avoided, and the yield will be improved.
• the water content in the cake can effectively be reduced, and the volume of the cake can be reduced, whereby it will be possible to conduct filtration by a filtration machine having a relatively small filtration capacity.
• the dispersibility as a feature of a disperse dye will not be impaired.
• a monoazodye having excellent dispersibility can be produced under an improved productivity.
• Example 1 To evaluate the stability with time as a disperse dye, the following test was conducted with respect to each of the cakes obtained in Example 1 and Comparative Example 2.
• the dispersibility of the powder before and after the accelerated test was evaluated as follows. Into a 150 ml polyethylene beaker, 1 g of the disperse dye composition powder and 99 ml of water were introduced and thoroughly stirred by a stirrer to obtain a uniform dispersion. Then, 100 ml of the disperse dye dispersion was filtered under suction at a reduced pressure of 150 mmHg (2.0 ⁇ 10 4 Pa) by a filter paper 5c (7 cm in diameter) manufactured by Toyo Filter Paper Company, whereby the time (sec) for filtration was examined. The results are shown in Table 2. Test Example 1 Test Example 2 Cake producing process Example 1 Comparative Example 2 Before the test 17 sec 18 sec After the test 19 sec 55 sec
• the volume of the cake was 4.7 ml/g, and the yield was 91.7%.
• a monoazo compound cake of the following formula was prepared in the same manner as in Example 1 except that in Example 1, 68 g of 2,4-dinitro-6-bromoaniline was changed to 56.3 g of 2,4-dinitro-6-chloroaniline. In this case, the volume of the cake was 2.5 ml/g, and the yield was 91.9%.
• a cake was prepared in the same manner as in Example 1 except that in Example 1, 4.5 g of polyoxyethylene-9-octadecenoic acid ester (HLB14) as a nonionic surfactant, was added after conducting the coupling reaction instead of adding it prior to the coupling reaction.
• HLB14 polyoxyethylene-9-octadecenoic acid ester
• the volume of the cake was 3.5 ml/g, and the yield was 92.3%.
• a monoazo compound cake of the following formula was prepared in the same manner as in Example 1 except that in Example 1, 93.5 g of N,N-bis(acetoxyethyl)amino-2-methoxy-5-acetanilide was changed to 97.2 g of N,N-bis(acetoxyethyl)amino-2-ethoxy-5-acetanilide. In this case, the yield was 91.8%, and the volume of the cake was 2.2 ml/g.
• Example 10 To evaluate the stability with time as a disperse dye, evaluation was conducted in the same manner as in Test Examples 1 and 2 with respect to each of the cakes obtained in Example 10 and Comparative Example 6. However, the composition of the wet cake and the dispersing agent was changed such that water was added to the wet cake (18 g as solid content), 24 g of Reax 85A® and 8g of Diadisperse® SW to bring the total amount to 500 g.
• the volume of the cake was 4.9 ml/g, and the yield was 89.6%.
• a monoazo compound cake of the following formula was prepared in the same manner as in Example 10 except that in Example 10, 40 g of 2,4-dinitro-6-bromoaniline was changed to 33.2 g of 2,4-dinitro-6-chloroaniline. In this case, the volume of the cake was 2.4 ml/g, and the yield was 90.1%.
• a cake was prepared in the same manner as in Example 10 except that in Example 10, 2.1 g of the polyoxyethylene-9-octadecenoic acid ester (HLB14) as a nonionic surfactant, was added after conducting the coupling reaction instead of adding it prior to the coupling reaction.
• HLB14 polyoxyethylene-9-octadecenoic acid ester
• the volume of the cake was 3.5 ml/g, and the yield was 89.6%.
• the diazotized solution obtained by the above diazotization reaction was dropwise added over a period of one hour at a temperature of from -5 to +5°C. Then, a coupling reaction was conducted at the same temperature for one hour to obtain a reaction mixture containing as the main component a monoazo compound of the following formula:
• the reaction mixture was heated to a predetermined temperature as identified in Table 4 over a period of one hour and then heat-treated at that temperature for 2 hours. Then, the mixture was cooled to 40°C and then filtered by means of a Nutsche funnel and washed with water. With respect to a cake recovered by the filtration, the yield and the volume of the cake were measured. Further, the foaming state during the heat treatment was observed. The results are shown in Table 4.
• a monoazo compound cake of the following formula was prepared in the same manner as in Example 18 except that in Example 18, 59.2 g of 2,6-dibromo-4-nitroaniline was used instead of 41.4 g 2,6-dichloro-4-nitroaniline, and the amount of polyoxyethylene-9-octadecenoic acid ester was changed to 3 g.
• Example 18 An azo compound cake was prepared in the same manner as in Example 18 except that in Example 18, 2.2 g of polyoxyethylene-9-octadecenoic acid ester (HLB14) as a nonionic surfactant, was added after the coupling reaction instead of adding it prior to the coupling reaction, and foaming, the volume of the cake and the yield were evaluated in the same manner. As a result, foaming was little, the volume of the cake was 2.20 ml/g and the yield was 96.2%.
• HLB14 polyoxyethylene-9-octadecenoic acid ester

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• 1993
  • 1993-03-23 TW TW082102168A patent/TW233304B/zh active
  • 1993-03-29 US US08/038,813 patent/US5532344A/en not_active Expired - Fee Related
  • 1993-03-31 MX MX9301850A patent/MX9301850A/es not_active IP Right Cessation
  • 1993-04-01 DE DE69321155T patent/DE69321155T2/de not_active Expired - Fee Related
  • 1993-04-01 BR BR9301399A patent/BR9301399A/pt not_active IP Right Cessation
  • 1993-04-01 EP EP93105453A patent/EP0563975B1/en not_active Expired - Lifetime
  • 1993-04-01 ES ES93105453T patent/ES2124269T3/es not_active Expired - Lifetime
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